CN103590089B - The preparation method of a kind of graphene/silver composite material - Google Patents
The preparation method of a kind of graphene/silver composite material Download PDFInfo
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Abstract
The present invention discloses the preparation method of a kind of graphene/silver composite material. Namely ultrasonic stripping graphite obtains graphene dispersing solution first in organic solvent, and then add silver ions salt in the graphene dispersing solution of gained, Graphene can adsorb the silver ions of interpolation and positively charged, then adopts electrophoretic deposition to prepare graphene/silver composite material. The preparation method of the present invention, Graphene adopts the ultrasonic stripping method preparation of liquid phase, and without oxide treatment, defect is less, remains the complete structure of Graphene; Using the electrophoretic deposition can in the evenly controlled deposition graphene/silver composite material of any three-dimensional conductive matrix surface, therefore the method has the advantages such as simple to operate, production cost is low, product homogeneity is good, easy to control.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, particularly relate to the preparation method of a kind of graphene/silver composite material.
Background technology
Since finding Graphene from 2004, just cause the extensive concern of researcher. Graphene has excellent mechanics, electronics, optics and thermal property, has great potential using value in fields such as microelectronics, stored energy, catalysis, biosensors. Due to the two-dimensional nanostructure of its uniqueness so that with the addition of the matrix material of Graphene and often there is excellent performance. Such as, document (Chem.Soc.Rev.2012,41,666-686) describes the application of a large amount of graphene composite material.
Silver nano material due to its special electronic structure and huge specific surface area make it the catalysis of chemical reaction, surface enhanced Raman scattering, sensor, biomarker, antibacterial etc. in have important application. Preparation about graphene/silver composite material is paid close attention to by many investigators, such as document (Chem.Commun.2011,47 (11), 3084-3086), (Nanoscale.2011,3 (3), 1182-1188) etc. a kind of method preparing graphene composite material is all reported.
The method preparing graphene/silver composite material at present is main mainly with solution phase chemical reduction, taking graphene oxide or reduced graphene as raw material, add certain dispersion agent and silver ions salt, make the suspension of evenly dispersion, add reductive agent again and make silver ion reduction, load on graphene sheet layer. It is that raw material also needs to reduce the matrix material obtained further according to graphene oxide, removes the oxy radical that surface of graphene oxide is a large amount of. But still there is the defect of more oxy radical in the Graphene peeled off through peroxidation, reduce every performance of Graphene after reduction. What also easily cause between graphene sheet layer in reduction process is stacking so that it is reunite. The reductive agent, the dispersion agent that add can remain in prepared material simultaneously, it is difficult to thoroughly remove.
The Graphene of band electric charge can be deposited to above the substrate of conduction by electrophoretic deposition, and mostly the mode of graphene ribbon electric charge is, and metal cation salt or ionogenic surfactant are added in employing in graphene dispersing solution, and Graphene adsorbed ion makes its own band electric charge. Patent CN102021633A proposes to add magnesium ion salt makes graphene ribbon electric charge, and patent CN102877109 proposes to adopt AMP as additive, is ionized by AMP and is adsorbed on Graphene and makes graphene ribbon electric charge. But above-mentioned patent just prepares simple graphene layer, it does not have consider to prepare graphene composite material by the method.
Summary of the invention
It is an object of the invention to solve above-mentioned technical problem and propose a kind of method adopting electrophoresis method to prepare graphene/silver composite material. For the destruction avoiding oxidising process graphene-structured to be brought, the present invention adopts the ultrasonic stripping Graphene of organic solvent, prepares graphene dispersing solution; Graphene ribbon electric charge is made by adding silver ions salt in solution; The method of electrophoretic deposition is finally taked to prepare one layer of controlled graphene/silver composite material on conducting base. Prepared graphene/silver composite material is evenly distributed, not containing other impurity, has potential using value at catalysis, photoelectric field.
The technical scheme of the present invention
A preparation method for graphene/silver composite material, specifically comprises the following steps:
(1), the preparation of graphene dispersing solution
In graphite: organic solvent 1 is the ratio of 1g:1L, being joined by graphite in organic solvent 1, control temperature 20-40 DEG C, power 200W carry out ultrasonic 2-20h, obtain dispersion liquid;
Then by the dispersion liquid of above-mentioned gained centrifugation 0.5-2h under the rotating speed of 4000r/min, supernatant liquid is graphene dispersing solution;
Because stripping conditions is different, the solids content in graphene dispersing solution is preferably 0.01-0.1g/L;
Described organic solvent is 1-Methyl-2-Pyrrolidone (NMP), tetrahydrofuran (THF) (THF), dimethyl formamide (DMF), butyrolactone (GBL), acetone or alcohol etc.;
Described graphite is Graphite Powder 99 or natural flake graphite, it is preferable to cross 32 order sieves;
(2), the preparation of band electric charge graphene dispersing solution:
In silver ions salt: organic solvent 2 is the ratio of 1g:1L, being dissolved in organic solvent 2 by silver ions salt and obtain silver ions salts solution, the organic solvent 1 that described organic solvent 2 is used in step (1) is identical;
The silver ions salts solution of above-mentioned gained is joined in the graphene dispersing solution of gained in step (1), concentration of silver ions is made to be 0.1-10mmol/L, control temperature 20-40 DEG C, power 200W carry out ultrasonic 30min to be made Graphene absorption silver ions and brings positive charge, obtains positively charged graphene dispersing solution;
Described silver ions salt is Silver Nitrate, silver chloride, Sulfuric acid disilver salt or Silver monoacetate;
(3), electrophoretic deposition prepares graphene/silver composite material
Using the electrolytic solution of the positively charged graphene dispersing solution of step (2) gained as electrophoretic deposition in electrophoretic deposition pond;
Using the anode pole piece of the conducting base of the metals such as metallic conduction matrix or coated copper, aluminium, nickel, stainless steel such as copper, aluminium, nickel or stainless steel or electro-conductive material as electrophoretic deposition pond;
Carry out electrophoretic deposition not limit the conductive substrates of its composition material and three-dimensional structure as cathode pole piece, deposit on cathode pole piece by the Graphene in positively charged graphene dispersing solution;
The described conductive substrates not limiting its composition material and three-dimensional structure is the metallic conduction matrixes such as copper, aluminium, stainless steel; Or the conducting base of the metal such as coated copper, aluminium, stainless steel or electro-conductive material; Or carbon fiber textile product are if carbon fiber paper, glassy carbon electrode, conductive polymers are such as nonmetal conducting bases such as polyanilines;
Then, by the cathode pole piece after electrophoretic deposition as 80 DEG C of oven drying 12h, namely obtain one layer graphene/silver composite material on the surface of cathode pole piece;
Above-mentioned electrophoretic deposition process control positive/negative plate spacing is 1-50mm, it is preferable to 5-10mm; Impressed voltage is 10-100V, it is preferable to 40-60V; Electrophoretic deposition process temperature is 40-120 DEG C, it is preferable to 50-70 DEG C; Time is 1-60min, it is preferable to 5-20min.
The useful effect of the present invention
The preparation method of a kind of graphene/silver composite material of the present invention, owing to adopting the method for electrophoretic deposition to prepare graphene/silver composite material, the method can be controlled in conductive substrates preparation one layer graphene/silver composite material, deposition can carry out in 3D structure, it is possible to preparation has the matrix material of multistage structure.
Further, the preparation method of a kind of graphene/silver composite material of the present invention, by regulating the experiment condition in the concentration of the solids content of Graphene with interpolation silver ions salt and deposition process, it is possible to control content and the microscopic appearance of final Graphene same silver simple substance. Further, owing to adopting the Graphene of ultrasonic stripping to avoid in oxidising process the defect introduced in preparation process, the mode of electrophoretic deposition makes silver particles evenly be compounded in graphene layer, avoids the agglomeration traits of Graphene.
Further, the preparation method of a kind of graphene/silver composite material of the present invention, has technique expanding production, simple operation and other advantages simple, easy.
Accompanying drawing explanation
The structural representation in Fig. 1, electrophoretic deposition pond 1 be direct supply, 2 is wherein positive pole, 3 be negative pole, 4 be tiselius apparatus, 5 for electrolytic solution;
The scanning electron microscope (SEM) photograph of the graphene/silver composite material of Fig. 2, embodiment 1 gained;
The scanning electron microscope (SEM) photograph of the graphene/silver composite material of Fig. 3, embodiment 2 gained;
The scanning electron microscope (SEM) photograph of the graphene/silver composite material of Fig. 4, embodiment 3 gained;
The Raman spectrum of the natural flake graphite used in Fig. 5, embodiment 1 and embodiment 2.
The Raman spectrum of the graphene/silver composite material obtained in Fig. 6, embodiment 1.
The Raman spectrum of the graphene/silver composite material obtained in Fig. 7, embodiment 2.
Embodiment
Below by specific embodiment and by reference to the accompanying drawings the present invention is set forth further, but do not limit the present invention.
The structural representation in electrophoretic deposition pond used in embodiments of the invention 1 be direct supply, 2 is wherein positive pole as shown in Figure 1,3 be negative pole, 4 be tiselius apparatus, 5 for electrolytic solution;
In embodiments of the invention, Raman spectrum test uses the silent Raman spectrometer (model DXRRamanMacroscope) flying your production of generation of U.S.'s match.
Scanning electron microscope used in the present invention is the S-3400N scanning electronic microscope that Hitachi produces.
Embodiment 1
A preparation method for graphene/silver composite material, specifically comprises the following steps:
(1), get 1g cross 32 orders sieve natural flake graphite, add 1L1-N-methyl-2-2-pyrrolidone N-, be placed in ultrasonic apparatus control temperature 20-40 DEG C, power 200W carry out ultrasonic 10h, obtain dispersion liquid;
Then by the dispersion liquid of above-mentioned gained centrifugation 1h under the rotating speed of 4000r/min, supernatant liquid is graphene dispersing solution;
(2), use 1-Methyl-2-Pyrrolidone be solvent, preparation 1g/L silver nitrate solution;
The silver ions salts solution of above-mentioned gained is joined in the graphene dispersing solution of gained in step (1), concentration of silver ions is made to be 1mmol/L, Graphene solids content is 0.02g/L, control temperature 20-40 DEG C, power 200W carry out ultrasonic 30min to be made Graphene absorption silver ions and brings positive charge, obtains positively charged graphene dispersing solution;
(3) electrolytic solution of the positively charged graphene dispersing solution prepared by 50mL step (2) as electrophoretic deposition pond, is got;
Using be polished to minute surface with the aluminum oxide powder of 1 micron, 0.3 micron, 0.05 micron successively glassy carbon electrode as cathode pole piece;
Electrophoretic deposition is carried out as anode pole piece using the nickel foil cleaned with the polishing of 6# abrasive paper for metallograph and with deionized water;
Above-mentioned electrophoretic deposition process control positive and negative plate spacing is 5mm, adds volts DS 60V, and depositing temperature is 40 DEG C, and depositing time is 10min, can at the surface preparation one layer graphene/silver composite material of glassy carbon electrode.
Embodiment 2
A preparation method for graphene/silver composite material, specifically comprises the following steps:
(1), graphene dispersing solution preparation process is with embodiment 1;
(2), use 1-Methyl-2-Pyrrolidone be solvent, preparation 1g/L silver nitrate solution;
The silver ions salts solution of above-mentioned gained is joined in the graphene dispersing solution of gained in step (1), concentration of silver ions is made to be 0.1mmol/L, Graphene solids content is 0.02g/L, control temperature 20-40 DEG C, power 200W carry out ultrasonic 30min to be made Graphene absorption silver ions and brings positive charge, obtains positively charged graphene dispersing solution;
(3), electrophoretic deposition process is with embodiment 1.
By the graphene/silver composite material of embodiment 1, embodiment 2 gained respectively with electron-microscope scanning, the scanning electron microscope (SEM) photograph of gained respectively as shown in Figure 2 and Figure 3, all can see that from Fig. 2,3 Graphene of lamella and the Argent grain without sizing mix uniformly. Comparison diagram 2 and Fig. 3, it is seen that improve concentration of silver ions used in preparation process and the silver content in the graphene/silver composite material of gained finally can be made to improve, and the particle diameter of Argent grain can be increased.
The Raman spectrum of the graphene/silver composite material of gained in natural flake graphite, the graphene/silver composite material of embodiment 1 gained and embodiment 2 that Fig. 5,6,7 are respectively in embodiment 1 and embodiment 2 to use, can see that from Fig. 5,6,7 graphene/silver composite material of gained in natural flake graphite raw material and embodiment 1, embodiment 2 all has three characteristic peaks, be positioned at 1580cm respectively-1G peak, be positioned at 1350cm-1Neighbouring D peak, and it is positioned at 2700cm-1Neighbouring 2D peak.
In the Raman spectrogram of the graphene/silver composite material of Fig. 6, Fig. 7 and embodiment 1, embodiment 2 gained, 2D peak is in single peak, and the You Jian peak, 2D peak of the natural flake graphite raw material used in Fig. 5 and embodiment 1 and embodiment 2 produces and peak position offsets to high wave number direction, this is the main difference of Graphene and graphite.
In the Raman spectrogram of the graphene/silver composite material of Fig. 6, Fig. 7 and embodiment 1, embodiment 2 gained, D peak is far above the D peak of the natural flake graphite raw material used in Fig. 5 and embodiment 1 and embodiment 2, this is owing to the ordered structure of graphite in ultrasonic procedure is destroyed, and shows that graphite flake layer is stripped.
In the Raman spectrogram of the graphene/silver composite material of Fig. 6, Fig. 7 and embodiment 1, embodiment 2 gained there is shoulder peak in G peak, this also illustrates graphite and is stripped into independent Graphene.
Fig. 6, Fig. 7 contrast, and can find out that the spectrogram intensity of embodiment 1 is much bigger compared with the spectrogram intensity of embodiment 2 further, and this is that what cause draws graceful reinforcing effect owing in embodiment 1, the matrix material silver content of gained is higher.
Embodiment 3
A preparation method for graphene/silver composite material, specifically comprises the following steps:
(1), graphene dispersing solution preparation process is with embodiment 1;
(2), band Graphene/Silver Nitrate dispersion liquid preparation process is with embodiment 1;
(3) electrolytic solution of the positively charged graphene dispersing solution prepared by 50mL step (2) as electrophoretic deposition pond, is got;
Using 400 order stainless steel meshs as cathode pole piece;
It is that anode pole piece carries out electrophoretic deposition and can obtain one layer graphene/silver composite material on the surface of cathode pole piece stainless steel mesh taking stainless steel;
400 above-mentioned order stainless steel meshs are 316 stainless steel steel, are cut to 1.5 �� 3cm2Size, successively with acetone, ethanol, deionized water ultrasonic cleaning 10min, immersing electrolytic solution area is 1.5 �� 1.5cm2;
Above-mentioned stainless steel anode pole piece 6# abrasive paper for metallograph polishing is also cleaned with deionized water;
Above-mentioned electrophoretic deposition process control positive and negative plate spacing is 5mm, adds volts DS 60V, and depositing temperature is 40 DEG C, and depositing time is 10min.
The scanning electron microscope (SEM) photograph of the graphene/silver composite material of above-mentioned gained as shown in Figure 4, as can see from Figure 4 Graphene/silver composite bed even compact to be deposited on stainless steel sift online, remain the three-dimensional structure of stainless steel mesh.
Embodiment 4
A preparation method for graphene/silver composite material, specifically comprises the following steps:
(1), graphene dispersing solution preparation process is with embodiment 1;
(2), use 1-Methyl-2-Pyrrolidone be solvent, preparation 1g/L Silver monoacetate solution;
The silver ions salts solution of above-mentioned gained is joined in the graphene dispersing solution of gained in step (1), concentration of silver ions is made to be 0.1mmol/L, Graphene solids content is 0.02g/L, control temperature 20-40 DEG C, power 200W carry out ultrasonic 30min to be made Graphene absorption silver ions and brings positive charge, obtains positively charged graphene dispersing solution;
(3) electrolytic solution of the dispersion liquid prepared by 50mL step (2) as electrophoretic deposition pond, is got;
It is anode pole piece taking stainless steel, with 1.5 �� 3cm2Carbon fiber paper be cathode pole piece, and to be immersed electrolytic solution area be 1.5 �� 1.5cm2Carry out electrophoretic deposition, one layer graphene/silver composite material can be obtained on the surface of carbon fiber paper;
Above-mentioned electrophoretic deposition process control positive and negative plate spacing is 10mm, and adding volts DS is 60V, and depositing temperature is 40 DEG C, and depositing time is 10min.
In sum, the preparation method of a kind of graphene/silver composite material of the present invention, can carry out in 3D structure and the original 3D structure of substrate can be retained, can effectively controlling the particle diameter of silver particles in matrix material by the concentration of silver ions in regulation and control solution, that draws that graceful sign presents Graphene clearly draws graceful absorption peak.
The above is only the citing of embodiments of the present invention; it is noted that for those skilled in the art, under the prerequisite not departing from the technology of the present invention principle; can also making some improvement and modification, these improve and modification also should be considered as protection scope of the present invention.
Claims (7)
1. the preparation method of a graphene/silver composite material, it is characterised in that specifically comprise the following steps:
(1) preparation of graphene dispersing solution
In graphite: organic solvent 1 is the ratio of 1g:1L, graphite joining ultrasonic 2-20h in organic solvent 1, ultrasonic temperature 20-40 DEG C of ultrasonic power 200W, obtains dispersion liquid;
Described graphite is Graphite Powder 99 or natural flake graphite;
The organic solvent 1 adopted is 1-Methyl-2-Pyrrolidone, tetrahydrofuran (THF), dimethyl formamide, butyrolactone, acetone or alcohol;
Then by the dispersion liquid of above-mentioned gained centrifugation 0.5-2h under the rotating speed of 4000r/min, supernatant liquid is graphene dispersing solution;
(2) preparation of band electric charge graphene dispersing solution:
In silver ions salt: organic solvent 2 is the ratio of 1g:1L, silver ions salt is dissolved in organic solvent 2 and obtains silver ions salts solution, described organic solvent 2 for the organic solvent 1 described in step (1) identical;
Described silver ions salt is Silver Nitrate, silver chloride, Sulfuric acid disilver salt or Silver monoacetate;
Being joined by the silver ions salts solution of above-mentioned gained in the graphene dispersing solution of gained in step (1), make concentration of silver ions be 0.1-10mmol/L, ultrasonic 30min makes Graphene absorption silver ions and brings positive charge namely to obtain positively charged graphene dispersing solution;
(3) electrophoretic deposition prepares graphene/silver composite material
Using the electrolytic solution of the positively charged graphene dispersing solution of step (2) gained as electrophoretic deposition in electrophoretic deposition pond;
With copper, aluminium, nickel or stainless steel, or using the substrate of coated copper, aluminium or stainless steel as the anode pole piece in electrophoretic deposition pond;
Electrophoretic deposition is carried out by cathode pole piece of the conductive substrates that do not limit composition material and three-dimensional structure, thus the Graphene in positively charged graphene dispersing solution is deposited on cathode pole piece, then cathode pole piece is placed in 80 DEG C of oven drying 12h, namely obtains one layer graphene/silver composite material on the surface of cathode pole piece;
Above-mentioned electrophoretic deposition process control positive/negative plate spacing is 1-50mm; Impressed voltage is 10-100V; Electrophoretic deposition process temperature is 40-120 DEG C; The electrophoretic deposition time is 1-60min.
2. the preparation method of a kind of graphene/silver composite material as claimed in claim 1, it is characterised in that the Graphite Powder 99 of to be Graphite Powder 99 or natural flake graphite the be 32 orders sieves of the graphite described in step (1) or natural flake graphite,
Solids content in the graphene dispersing solution of gained is 0.01-0.1g/L.
3. the preparation method of a kind of graphene/silver composite material as claimed in claim 2, it is characterised in that in step (1), the solids content in the graphene dispersing solution of gained is 0.02g/L.
4. the preparation method of a kind of graphene/silver composite material as claimed in claim 3, it is characterized in that the control positive/negative plate spacing of the electrophoretic deposition process described in step (3) is 5-10mm, impressed voltage is 40-60V, and electrophoretic deposition process temperature is 50-70 DEG C, and the time is 5-20min.
5. the preparation method of a kind of graphene/silver composite material as claimed in claim 4, it is characterized in that the control positive/negative plate spacing of the electrophoretic deposition process described in step (3) is 5-10mm, impressed voltage is 60V, and electrophoretic deposition process temperature is 40 DEG C, and the electrophoretic deposition time is 10min.
6. the preparation method of a kind of graphene/silver composite material as claimed in claim 5, it is characterised in that the conductive substrates not limiting its composition material and three-dimensional structure described in step (3) is copper, aluminium or stainless steel; Or be the conducting base of coated copper, aluminium or stainless steel; Or be nonmetal conducting base, described nonmetal conducting base is carbon fiber textile product, glassy carbon electrode or conductive polymers.
7. the preparation method of a kind of graphene/silver composite material as claimed in claim 6, it is characterised in that described carbon fiber textile product are carbon fiber paper; Described conductive polymers is polyaniline.
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| CN104217907A (en) * | 2014-09-12 | 2014-12-17 | 中国科学院深圳先进技术研究院 | Preparation method for graphene field emitting cathode, and graphene field emitting cathode |
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| CN109554628B (en) * | 2018-11-23 | 2020-04-28 | 中国航发北京航空材料研究院 | Preparation method of graphene composite high-speed tool steel |
| CN110739436A (en) * | 2019-10-28 | 2020-01-31 | 昆山宝创新能源科技有限公司 | Graphene-silver composite tab, preparation method thereof and lithium battery pole piece |
| CN112310401A (en) * | 2020-11-03 | 2021-02-02 | 天津大学 | Preparation method of lithium ion battery negative electrode material and conductive agent |
| CN112708918B (en) * | 2020-12-11 | 2021-10-08 | 南方医科大学口腔医院 | Antibacterial and corrosion-resistant orthodontic metal appliance and preparation method thereof |
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| CN102061495A (en) * | 2010-11-15 | 2011-05-18 | 沈阳工业大学 | Graphite dispersant agent in cyanide-free electrodeposition silver-graphite alloy plating solution and preparation method |
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